Optically active high-molecular compounds

ABSTRACT

Disclosed are optically active high-molecular-weight compounds of the following formula 
                         
and stationary-phase materials containing the same. The high-molecular-weight compounds exhibit optical activity by virtue of their stacking helical structure wherein the aromatic groups are aligned in a twisted arrangement, thus being useful as optically active stationary phases for HPLC or polarized- light absorbers.

FIELD OF THE INVENTION

This invention relates to high-molecular-weight compounds which havearomatic groups such as fluorine residue in a side chain. In particular,it relates to high-molecular-weight compounds which exhibit opticalactivity by virtue of their stacking helical structure wherein thearomatic groups are aligned in a twisted arrangement, thus being usefulas optically active stationary phase for HPLC or polarizationabsorption-light emitting materials, and a stationary phase materialusing the same.

BACKGROUND OF THE INVENTION

As described in Nakano, Preliminary reports of the 48th Annual Meetingof the Society of Polymer Science, Japan (Polymer Preprints, Japan, 48,(7), 1279(1999)), it is known that dibenzofulvene polymerizes and apolymer is obtained. However, in this case, the polymer does not showoptical activity, because the polymerization-initiating agent which isnot an optically active species is used. On the other hand, as describedin “Generalities of Chemistry” No. 18, page 129-136 (1993), it is knownthat poly(triphenylmethyl methacrylate) shows optical activity. But thispolymer has poor solvent-resistance, therefore, it is disadvantageous touse the polymer as an optically active stationary phase for HPLC. Asdescribed in Tokkai 2001-106729, an optically active maleimide polymeris already known. This polymer is excellent in solvent-resistance,however, it has disadvantage that its separation ability is poor.

The inventor made a detailed study on giving an optical activity topolymers of the above-mentioned dibenzofulvene or similar compoundsthereof which are excellent in solvent-resistance. As a result, it wasdiscovered that when dibenzofulvene or similar compounds thereof arepolymerized by using an anionic polymerization initiator having anoptically active alkyl group together with a chiral ligand, or when anoptically active group-introduced dibenzofulvene or similar compoundsthereof are polymerized by using an anion polymerization initiator, theobtained high-molecular-weight compounds show optical activity becausemain chains of them have a helical structure, which led to the presentinvention.

It is therefore a first object of this invention to provide ahigh-molecular-weight compound having excellent solvent resistance andshowing optical activity.

It is a second object of this invention to provide an optically activestationary phase applicable to HPLC, having excellent solventresistance.

SUMMARY OF THE INVENTION

The aforesaid objects of this invention are attained by optically activehigh-molecular-weight compounds represented by the following structuralformula 1. When the high-molecular-weight compounds of this inventionare used for an optically active stationary phase or the like, thehigh-molecular-weight compounds represented by the following structuralformula 2 are preferable.

In the formula, Ar is an aromatic ring, R¹ and R² are hydrogen atoms ororganic groups, however, hydrogen atoms, alkyl groups, aromatic groups,—CN or ester groups are preferable. n is an integer of 2 or more,preferably 2-5,000 and 4-1,000 is most preferable.

X is a group selected from among —(CH₂)_(m)—, aromatic groups, vinylenegroups, hetero atoms and functional groups containing hetero atoms. m isan integer of 0 or more.

R³ and R⁴ are substituents, and preferably hydrogen atoms, alkyl groups,aromatic groups, carboxyl groups, ester groups, ether groups, functionalgroups having an urethane bond, halogen atoms, hetero atoms, functionalgroups bonding to aromatic group through hetero atom, —CN and —(C═O)R,wherein R is a hydrogen atom, a hetero atom or an organic group. R³ andR⁴ may be introduced 2-4 times respectively. Each of R³ and R⁴ may beidentical with or different from each other.

Further, R³ and R⁴ may be optically active functional groups. Theoptically active functional group is a functional group having anasymmetric carbon atom, or having neither a plane of symmetry nor S2symmetry.

In formula 2, n, R¹ and R² are the same as those of n, R¹ and R² informula 1 and R³-R¹⁰ are the same groups as R³ and R⁴ in formula 1.

BRIEF DESCRIPTION OF THE DRAWINGS

(FIG. 1)

A theoretical C,D spectra of an initiation terminal model (A) and adimmer B of polymer model, and an observed CD spectrum (F) of thepolymer obtained in the example.

MOST PREFERRED EMBODIMENT OF THE INVENTION

As a method obtaining a polymer described in claim 1 represented by thefollowing structural formula 1, anionic polymerization is preferable,wherein anionic polymerization initiator having an optically activealkyl group or anionic polymerization initiator together with a chiralligand is used.

The above-mentioned Ar is an aromatic ring, R¹ and R² are hydrogen atomsor organic groups. Preferable R¹ and R² are hydrogen atoms, alkylgroups, aromatic groups, —CN or ester groups, but hydrogen atoms, alkylgroups of C₁-C₁₀, phenyl groups and —CN are more preferable. n is aninteger of 2 or more, but preferably 2-5,000 and more preferably4-1,000. If n is less than 2, a stacking structure is not formed and ifn is more than 5,000, the synthesis is difficult.

X is a group selected from among —(CH₂)_(m)—, an aromatic group, avinylene group, a hetero atom or a group containing a hetero atom, and mis an integer larger than O. As an example of the hetero atom of X, —O—,or —S— can be mentioned. As an example of the group containing a heteroatom, —NR— or —C(O)— etc. can be mentioned.

R³ and R⁴ are substituents and they are preferably hydrogen atoms, alkylgroups, aromatic groups, carboxyl groups, ester groups, ether groups,functional groups having a urethane bond, halogen atoms, functionalgroups linked with an aromatic group through a hetero atom, —CN or—(C═O)R. The hetero atom is N, S or O. In the present invention,particularly, hydrogen, an alkyl group having 1-20 carbon atoms, anaromatic group having 6-30 carbon atoms, a carboxyl group, an estergroup having 2-30 carbon atoms, an ether group having 2-30 carbon atoms,a functional group of 2-30 carbon atoms having an urethane bond, F, Cl,Br, I, —NRR′, —SR, —OR, —NO₂, —CN or a functional groups representedbelow are preferable, wherein R and R′ are hydrogen atoms, hetero atomsor organic groups.

In the formulae, R″, R′″ and R″″ are hydrogen atoms or organic groups.

Further, R³ and R⁴ may be the optically active functional groups. Theoptically active functional group is a functional group having anasymmetric carbon atom, or having neither a plane of symmetry nor S2symmetry.

R³ and R⁴ may be introduced 2-4 times respectively. In this case, R³ andR⁴ may be identical with or different from each other.

Aforesaid anionic polymerization initiators having an optically activealkyl group are shown in 1 and 2 below, and aforesaid anionicpolymerization initiators together with a chiral ligand are shown in 3below.

1. R*M

In this case, R* is an optically active alkyl group and M is an alkalimetal or alkaline earth metal. As an example of R*M, (−)—menthoxypotassium and (+)—menthoxy potassium can be mentioned.

2. RR*NM and RR*RM

In this case, R is an alkyl group, R* is an optically active alkylgroup, M is an alkali metal or alkaline earth metal and N is a nitrogenatom. As examples of them, compounds below can be mentioned.

3. ROM/Chiral Ligand

In this case, R is an alkyl group, O is an oxygen atom, M is an alkalimetal or alkaline earth metal. The chiral ligand is a diamino compoundcontaining an optically active group and can be a bidentate ligand.Examples thereof are (+)—or (−)—sparteine, (+) —or(−)—1,4—bis(dimethylamino)—2,3—dimethoxybutane, (+) —or(−)—(1—pyrrolidinylmethyl)pyrrolidine, (+) —or(−)—(4S)—2,2′—(1—ethylpropylidene)bis[4—(1—phenylethyl)—4,5—dihydroxazole].

4. RM/R′XM′ Complex

In this case, R is an alkyl group, X is an oxygen atom or nitrogen atom,M is an alkali metal or alkaline earth metal. R′ is an optically activegroup. M′ is an alkali metal or alkaline earth metal, which is identicalwith or different from M. Examples of R′X are (+) —or (−)—menthoxygroup, 1—phenylethylamino group, 1—naphthylethylamino group and2—(1—pyrrolidinylmethyl)pyrrolidine—1—yl group.

The above-mentioned anionic polymerization initiators may be used aloneor in combination. When R³ or R⁴ in the formula 1 or R³-R¹⁰ in formula 2are groups which do not have an optically active group, it is necessaryto use these anionic polymerization initiators. However, a monomer offormula 1 having an optically active substituent which is introduced asR³ or R⁴ is used, a common anionic polymerization initiator which has nooptical activity can be used, however, it is preferable to use theoptically active anionic polymerization initiator. That is, even whenpolymerization initiators with no optical activity are used, a polymerhaving a stable optical activity is obtained, since a stacking structureof a side chain of the polymer is twisted because of an interactionbetween said optically active substituents.

Molecular weight of the polymer of the present invention is preferably500-1 million in terms of number average molecular weight. If themolecular weight is 500 or less, a solvent resistance is low. It isdifficult to polymerize so that-the molecular weight is 1 million ormore. A variance degree of molecular weight is preferably 1-3,particularly, 1-2 is more preferable. When the polymer having thevariance degree of more than 3 is used as a stationary phase of a HPLC(high performance liquid column chromatography), separation ability ofHPLC is poor.

The polymer of the present invention may be a copolymer obtained bypolymerization with other polymerizable compound. Aforesaid otherpolymerizable compound is preferably a compound capable of anionicpolymerization. Examples of the compound are acrylate a methacrylate,aminoalkyl acrylate such as N,N-dimethylaminoethyl acrylate,N,N-diethylaminoethyl acrylate and N,t-butylaminoethyl acrylate;(meth)acrylonitrile; butadiene; isoprene; a vinyl chloride; vinylidenechloride; vinyl acetate; vinyl ketone; N-vinylpyrrolidone;vinylpyridine; (meth)acrylamide; styrene compounds such asdivinylbenzene; α-methylstyrene, vinyltoluene, chlorostyrene,t-butylstyrene and styrene; fumaric acid; maleic acid; itaconic acid;phthalic acid; monoalkyl esters of fumaric acid, dialkyl esters offumaric acid; monoalkyl esters of maleic acid, dialkyl esters of maleicacid; monoalkyl esters of itaconic acid, dialkyl esters of itaconicacid; monoalkyl esters of phthalic acid, and dialkyl esters of phthalicacid. In addition, the copolymerization is, preferably a blockcopolymerization.

Further, a polymerizable compound having two functional groups or morecan be copolymerized. Thus, properties such as a solvent resistance canbe improved. A polymerizable compound having a photo polymerizablyfunctional group can be copolymerized to cross link each other by aradiation of light after the copolymerization.

A stationary phase material described in claim 7 is a powder of thepolymer compound itself of the present invention or a material obtainedby coating the polymer compound of the present invention on a surface ofa particle carrier. Examples of these materials are as follows;

-   1. A material obtained by crashing a polymer into powder wherein the    polymer is one described in claim 1 or 2 and insoluble in a solvent.    Particularly, an average diameter is preferably uniform.-   2. A material wherein the polymer described in claim 1 or 2 is    embedded or chemically bonded to a surface of a silica-gel or    alumina.-   3. A material wherein the polymer described in claim 1 or 2 is    embedded or chemically bonded to a surface of a styrene bead.

EXAMPLES

Hereafter, this invention will be described in further detail referringto examples, but this invention is not to be construed as being limitedin any way thereby.

Example 1 Polymerization of Dibenzofulvene using Menthoxy PotassiumPreparation of Initiator (Menthoxy Potassium)

0.3 g of KH (suspended in a paraffin) was introduced into a flame-driedample wherein an air had been replaced by nitrogen. 10 ml of dried THFwas introduced to the ample, thereby washing off the paraffin from KHand an upper liquid was removed by using a syringe. After repeating thisoperation three times, the resultant remainder was dried under a vacuum.(−)-menthol (312.5 mg, 2.00 mmol) was introduced into the ample andcarried out the reaction, primarily, at room temperature for 2 hours,after that, at 50° C. for 3 hours. An upper liquid of the obtainedreaction mixture was used as a polymerization initiator.

Polymerization

Dried THF solution of dibenzofulvene (0.46M, 4.4 ml, 2.02 m mol) wasintroduced into a flame-dried ample wherein an air had been replaced bynitrogen. The solution was further diluted by adding a dried THF (3.8ml). After cooling the solution to −78° C., the THF solution of menthoxypotassium (2.0 ml of 0.2M), which was obtained by above-mentioned mannerwas added to initiate the polymerization and kept the solution still at−78° C. for 24 hours. After 24 hours, a methanol (0.2 ml) was added tothe reaction mixture to stop the polymerization while keeping thetemperature at −78° C.

A part of the reaction mixture was diluted with CDCl₃, then the ¹H-NMRwas measured, and the monomer conversion ratio was determined (monomerconversion ratio: >99%) from the intensity ratio of the absorption peakof the solvent used as internal reference to that of the vinyl proton inthe remaining monomer. The solvent was distilled off from the reactionmixture to obtain a crude product. From the crude product, THF insolublefraction (285.8 mg, 68%) and a THF soluble fraction were separated.Further, MeOH was added into the THF soluble fraction to reprecipitateand to obtain MeOH insoluble product (35.0 mg, 8%).

The THF-soluble, MeOH-insoluble fraction: Molecular weight: Mn=1070,Mw/Mn=1.47 (GPC, vs. polystyrene);

Absorption spectra: ε=1960 (300 nm), ε=5739 (264 nm), ε=4559 (241 nm)[THF 25° C.];

circular dichroism: [θ]=176 (300 nm), [θ]=−738 (264 nm): [θ]=962 (241nm) [THF, 25° C.];

optical rotation: [α]₃₆₅ =0° (THF, C=0.30, 23° C.) [reference data(optical rotation of (−)-menthol): [α]₃₆₅ =−149° (THF, C =0.49, 22° C.)]

By comparing the C,D spectra of the polymer obtained from the aboveexperiment and C,D spectra obtained from theoretical simulation based onan assumption of torsional structure, it was proved that the polymerobtained from the above experiment had a torsional structure.

Theoretical simulation 1: The most stable conformation of9-menthoxy-9-methyl fluorene, as a model compound of initiationterminal, was obtained by Monte Carlo simulation using MMFF field. MacroModel manufactured by Schroedinger co.,ltd was used for the simulation.An expected C,D spectra for the conformation was calculated by thesemiempirical molecular orbital method INDO/S (FIG. 1A). For thecalculation, the program provided by Dr. J. Downing of ColoradoUniversity was used (G. Bringmann etc, J. Am. Chem. Soc., 123,2703-2711). Subsequently, as the polymer model, a dimer model wassimulated and an expected C,D spectra for each model having dihedralangles Φ1 and Φ2 of 175°, 170°, 160° or 150° was calculated by thesemiempirical molecular orbital method INDO/S (FIG. 1B-E). The actualspectrum (FIG. 1F) completely differed from that of the initiationterminal model (FIG. 1A). Thus, it was found that C,D spectra of thepolymer obtained in the Example were not caused by menthoxy group atterminal of the polymer but were derived from the torsions of amain-chain (helical structure) of the polymer. Further, as the spectrumof FIG. 1F coincides well to C,D spectra of FIG. 1, it, is clarifiedthat the torsion of main-chain has a dihedral angle of 170°-160°.

Example 2 Asymmetric Polymerization of 2,7-n-pentylDBF by Sp-F1LiPreparation of Initiator

Fluorene (169.2 mg, 1.02 mol) was dissolved into a dried toluene (4.0ml) in a flame-dried ample wherein an air had been replaced by nitrogen.A hexane solution of n-BuLi (1.6M, 0.64 ml) was slowly added into theobtained solution. After 30 minutes from the addition at roomtemperature, (−)-sparteine (0.28 ml) was introduced to the ample. Aftershaking and agitating, the mixture was kept still for 10 minutes. Thusobtained reaction mixture was used as a polymerization initiator.

Polymerization

A dried hexane solution of 2,7-dipentyldibenzofulvene (0.97M, 1.05 ml,1.02 mmol) was introduced into a flame-dried ample wherein an air hadbeen replaced by nitrogen, then hexane was distilled off. A driedtoluene (4.5 ml) was added to dissolve the monomer, then the solutionwas cooled to −78° C. and the initiator (0.2M, 0.25 ml) already preparedwas added to the solution, thereby a polymerization started. Thepolymerization reaction was carried out for 24 hours at −78° C. Afterthat, methanol (0.2 ml) was added to the reaction mixture while keepingat −78° C. to stop the polymerization.

After a fraction of the reaction mixture was diluted with CDCl₃, the¹H-NMR was measured, and the monomer conversion ratio was determined(monomer conversion ratio: 80%), from the intensity ratio of theabsorption peak of the solvent used as internal reference to that ofabsorption of the vinyl proton in the remaining monomer.

The solvent was distilled off from the reaction solution to obtain acrude product. From the crude product, a THF insoluble fraction (90.5mg, 27%) and a THF soluble fraction were separated. Further, MeOH wasadded into the THF soluble fraction to reprecipitate, and to obtain MeOHinsoluble fraction (104.1 mg, 31%).

The THF-soluble, MeOH-insoluble fraction: Molecular weight, Mn=3600,Mw/Mn=1.17 (GPC, vs. polystyrene);

Absorption spectra: ε=11841 (282 nm), ε=12212 (274 nm) [THF, 25° C.][reference data (monomer unit model, 2,7-n-phenylfluorene): ε=20436 (282nm), ε=28315 (274 nm) [THF, r.t.]];

emission spectra, λ_(max)=403 nm, [λ_(Ex)=282 nm, THF, r.t.]];[reference data (monomer unit model, 2,7-n-phenylfluorene): λ_(max)=315nm [Ex.=282 nm, THF, r.t.];

circular dichroism, [θ]=−73, (318 nm): [θ]=426 (288 nm), [θ]=−450 (253nm) [THF, 25° C.];

optical rotation [α]₃₆₅=−16 ° (THF, C=0.40, 22° C.)

Example 3 Polymerization of iBu-DBF by Sp,DDB-F1Li Polymerization

2,7-diisobutyldibenzofulvene (291.0 mg 1.00 mmol) was dissolved into adried toluene (4.5 ml) in a flame-dried ample wherein an air had beenreplaced by nitrogen. The solution was cooled to −78° C. and a solutionof the initiator prepared in Example 2 (0.2M, 0.25 ml) was added,thereby a polymerization started. The polymerization reaction wascarried out for 24 hours at −78° C. MeOH (0.2 ml) was added to thereaction mixture while keeping at −78° C. to stop the polymerization. Apart of the reaction mixture was diluted with CDCl₃, then the ¹H-NMR wasmeasured, and the monomer conversion ratio was determined (monomerconversion ratio: 41%) from the intensity ratio of the absorption peakof the solvent used as internal reference to that of the vinyl proton inthe remaining monomer. The solvent was distilled off from the reactionmixture to obtain a crude product. From the crude product, a THFinsoluble fraction (19.3 mg, 7%) and a THF soluble fraction wereseparated. Further, MeOH was added into the THF soluble fraction toreprecipitate and to obtain MeOH-insoluble fraction (120.1 mg, 40%).

The THF-soluble, MeOH-insoluble fraction: Molecular weight, Mn=3300,Mw/Mn=1.10 (GPC, vs. polystyrene);

Absorption spectra, ε=11244 (294 nm), ε=10574 (274 nm) [THF, 25° C.][reference data (monomer unit model, 2,7—n—phenylfluorene): (ε=7074 (294nm), ε=30021 (274 nm) [THF, r.t.]);

Emission spectra, λ_(max)=405 nm [Ex.=294 nm, THF, r.t.,] [referencedata (monomer unit model, 2,7-iso-butylfluorene); λ_(max)=315 nm[Ex.=294 nm, THF, r.t.];

Circular dichroism, [θ]=604 (319 nm), [θ]=−289 (285 nm), [θ]=500 (255nm)] [THF, 25° C.]:

Optical rotation, [α]₃₆₅=+31° (THF, C=0.37, 25° C.).

Example 4 Chiral Separation of the Polymer Produced in Example 1

A THF-insoluble product (10 mg) of the polymer produced in Example 1 wascrushed in a mortar and introduced in a glass tube with a screw cap.After an addition of ethanol solution (0.5 mg/ml, 100 μl (solute: 0.05mg)) containing racemic body of trans-stilbene oxide, Tröger's base andflavanone, the glass tube was sealed and kept still at room temperature(23° C.). 10 μl of a solution part in the tube was analyzed by an HPLChaving a chiral column (Chiral cell OD—H, Daicel chemical industries,ltd., eluent: hexane/2—propanol (95/5)) Then, an adsorption amount andan optical purity of the solution part were determined and separationfactors α₁ and α₂ were calculated (table 1).

In the table, the separation factors were calculated by the followingexpressions based on the two definitions. The polymer showed anasymmetric separation ability for each racemic body.

-   α₁={(major antipode in the solution (%))/(minor antipode in the    solution(%))}-   /{(major antipode in the sample adsorbed (%))/(minor antipode in the    sample adsorbed (%))}-   ={(major antipode in the solution (%) )/(minor antipode in the    solution(%)}-   /{(50-major antipode in the solution (%))/(50-minor antipode in the    solution(%))}    wherein-   major antipode in the solution (%) =(100-adsorption rate    (%))×(100+|optical purity of the sample in the solution|)/2×1/100,-   minor antipode in the solution (%) =(100-adsorption rate    (%))×(100+|optical purity of the sample in the solution|)/2×1/100-   α₂=(major antipode in the solution (%))-   /(minor antipode in the solution (%))

TABLE 1 An asymmetric separation ability of polymer obtained in Example1^(a) Optical Adsorp- purity of Separation Racemic tion Adsorptionsolute in the factor Test body period rate^(a) (%) solution α₁ α₂ 1Trans- 38 22.7 6.2 1.73 1.13 stilbene 2 oxide tröger's 18 8.9 1.6 1.411.03 base 3 flavanone 18 37.1 7.2 1.47 1.15 ^(a)adsorption test at roomtemperature

Comparative Example 1

0.5 m mol of dibenzofulvene was dried under vacuum for 30 minutes, thendissolved it in 3 ml of THF which had been distilled to remove air. Tothe obtained solution, 0.025 m mol of n-BuLi as a polymerizationinitiator was added and a reaction was carried out for 24 hours at −78°C. 2 ml of methanol was added to the solution to stop the reaction, thena hexane-insoluble fraction was obtained by using a centrifugalseparator.

When optical rotation was measured in the same manner as the Example,the optical rotation was 0°.

INDUSTRIAL APPLICABILITY

The high-molecular-weight compound having optical activity of thepresent invention has an excellent solvent resistance, therefore, it issuitable for an optically active stationary phase applicable to HPLC andfor a polarization absorption-light emitting material.

1. An optically active high-molecular-weight compound of the followingformula

wherein, Ar is a benzene ring, R¹ R² are, each independently, hydrogen,—CN, an alkyl group, or an ester group, R³ and R⁴ are, eachindependently, hydrogen, halogen, an alkyl group, carboxyl group, estergroup, ether group, —CN or —(C═O)R, n is an integer of 2 to 5000, X is—(CH₂)_(m)—, a vinylene group, N, S, O, —NR—or —C(O)—, m is an integerof 0 or 1, R³ and R⁴ may be introduced 2-4 times respectively, whereinthese may be identical or different, and R is hydrogen, N, S or O, whichcompound is optically active.
 2. An optically activehigh-molecular-weight compound according to claim 1, wherein n is aninteger of 4 to
 1000. 3. An optically active high-molecular-weightcompound according to claim 1, which is a copolymer obtained bypolymerization reaction of compounds having two or more polymerizablyfunctional groups.
 4. An optically active high-molecular-weight compoundaccording to claim 1, which is a crosslinked polymer.
 5. An opticallyactive high-molecular-weight compound according to claim 1, wherein R¹and R² are, each independently, hydrogen, an alkyl group having 1 to 10carbon atoms, or —CN.
 6. An optically active high-molecular-weightcompound according to claim 1, wherein R³ and R⁴ are, eachindependently, hydrogen, an alkyl group having 1-20 carbon atoms, acarboxyl group, an ester group having 2-30 carbon atoms, an ether grouphaving 2-30 carbon atoms, F, Cl, Br, I or —CN.
 7. An optically activehigh-molecular-weight compound according to claim 1, wherein R³ andR⁴are, each independently, hydrogen, an alkyl group having 1-20 carbonatoms, a carboxyl group, an ester group having 2-30 carbon atoms, anether group having 2-30 carbon atoms, F, Cl, Br, I, —CN, or

wherein R″″ is hydrogen.
 8. An optically active high-molecular-weightcompound according to claim 1, wherein m is
 1. 9. An optically activehigh-molecular-weight compound according to claim 1, wherein X is—(CH₂)_(m)—, and m is
 0. 10. An optically active high-molecular-weightcompound according to claim 1, wherein R is hydrogen or O.
 11. Astationary phase material, comprising a high-molecular-weight compoundaccording to claim
 1. 12. An optically active high-molecular-weightcompound according to claim 1, wherein X is —(CH₂)_(m)-, N, S, O, —NR—or—C(O)—.
 13. An optically active high-molecular-weight compound accordingto claim 1, wherein R¹ and R² are, each independently, hydrogen, or —CN.14. An optically active high-molecular-weight compound according toclaim 1, wherein R¹ and R² are, each independently, hydrogen, or analkyl group having 1 to 10 carbon atoms.
 15. A stationary phasematerial, comprising a high-molecular-weight compound according to claim9.
 16. A stationary phase material according to claim 11, which isprepared by embedding or fixing through a chemical bond saidhigh-molecular-weight compound on a silica-gel, an alumina orpolystyrene bead.